This invention relates to fluorochemical polymers for use in providing stain release properties to a substrate material. In another aspect, this invention relates to fluorochemical polymers that contain pendant fluoroaliphatic and cationogenic groups. This invention also relates to fluorochemical polymers with improved stain release durability when applied to a substrate material.
The treatment or modification of fabrics to improve their properties is routine practice in the textile industry. Fabrics can be treated to reduce their oleophilicity and facilitate stain release during laundering. Such treatments include fluorochemical-based polymers containing both fluorinated oleophobic and non-fluorinated hydrophilic fractions.
Fluorochemicals include substances containing portions which are fluorocarbon in nature and portions which are organic hydrocarbon in nature. Such fluorochemicals are common and have various industrial uses including reducing the surface tension of liquids, reducing evaporation and flammability of volatile organic liquids, and improving the leveling of organic polymer coatings.
The utility of organofluorine compounds as surface-active agents and surface-treating agents is due in large part to the extremely low free-surface energy of a C6-C12 fluorocarbon group, according to H. C. Fielding, xe2x80x9cOrganofluorine Compounds and Their Applicationsxe2x80x9d R. E. Banks, Ed., Society of Chemical Industry at p. 214 (1979).
Generally, the present invention relates to fluorochemical polymers for use in providing stain release properties to a substrate material. One embodiment is a polymer that includes, i) a perfluoroaliphatic monomer of the formula 
where Rf is a C1-C20 perfluorinated group, A is divalent linking group, 
group, z is 1 to 12, m is 1 to 6, n is 1 to 12, R1 is H or CH3xe2x80x94, and R2 is H, CH3xe2x80x94 or C2H5xe2x80x94; ii) a hydrophilic monomer of the formula 
where B is a divalent linking group, R3 is H or CH3, p is 1 to 25, R4 is C1-C12 alkyl, aryl, aralkyl or alkaryl; iii) a cationogenic monomer of the formula 
where L is xe2x80x94(CqH2q)xe2x80x94Y, and salts thereof, i.e. xe2x80x94(CqH29q)xe2x80x94Y+ Xxe2x88x92 q is 1 to 8, Y is a cationogenic group, Xxe2x88x92 is an anion, R5 is H or CH3xe2x80x94, and R6 and R7 are independently C1-C12 alkyl or C1-C2 hydroxyalkyl; and iv) a N-hydroxyalkylacrylamide monomer of the formula 
where z is 1 to 12, and R11 is H or CH3xe2x80x94; and/or v) a diacrylate monomer of the formula 
where R12 is H or CH3xe2x80x94, and R13 includes xe2x80x94(CH2CH2O)pxe2x80x94, where p is 1 to 25.
An embodiment of the present invention includes polymers described above where monomer (i) is present in the amount of 20 to 70 percent by weight, monomer (ii) is present in the amount of 25 to 60 percent by weight, monomer (iii) is present in the amount of 1 to 20 percent by weight, and monomer (iv) is present in the amount of 1 to 10 percent by weight.
Another embodiment of the present invention includes polymers described above where monomer (i) is present in the amount of 45 to 70 percent by weight, monomer (ii) is present in the amount of 25 to 50 percent by weight, monomer (iii) is present in the amount of 1 to 10 percent by weight, and monomer (iv) is present in the amount of 1 to 8 percent by weight.
A further embodiment of the present invention includes polymers described above where monomer (i) is present in the amount of 50 to 65 percent by weight, monomer (ii) is present in the amount of 35 to 40 percent by weight, monomer (iii) is present in the amount of 1 to 5 percent by weight, and monomer (iv) is present in the amount of 1 to 5 percent by weight.
An embodiment of the present invention includes polymers described above where monomer (i) is present in the amount of 20 to 70 percent by weight, monomer (ii) is present in the amount of 25 to 60 percent by weight, monomer (iii) is present in the amount of 1 to 20 percent by weight, and monomer (v) is present in the amount of 0.001 to 5 percent by weight.
In an additional embodiment, monomer (i) is present in the amount of 45 to 65 percent by weight, monomer (ii) is present in the amount of 30 to 50 percent by weight, monomer (iii) is present in the amount of 1 to 10 percent by weight, and monomer (v) is present in the amount of 0.01 to 2 percent by weight.
In yet a further embodiment, monomer (i) is present in the amount of 50 to 60 percent by weight, monomer (ii) is present in the amount of 35 to 45 percent by weight, monomer (iii) is present in the amount of 1 to 5 percent by weight, and monomer (v) is present in the amount of 0.1 to 1 to percent by weight.
Yet another embodiment, of the present invention includes a composition for imparting oil, water and stain repellency and stain-release properties to a substrate including an aqueous, substantially organic solvent free, solution or dispersion of the polymers described above.
Advantageously, the polymers of the present invention may be applied to substrates, such as textiles, to provide stain resistance, stain release and or oil-repellency without the use of other common textile additives such as permanent press resins, and the like. However, such additives may be added where desired. Such additives may be admixed with the polymers of the invention and applied to the substrate, or may be applied separately.
An additional advantage of the present invention is that aqueous solutions of the polymers described herein maintain a water-like viscosity characteristic which allows the materials to be conveniently handled and transferred even at wt solids at or above 15%. This allows for more efficient conveyance of polymer solutions, since a higher percent solids aqueous formulation necessarily requires the transportation of less water.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. As used herein, the term polymer shall be inclusive of oligomers. The detailed description which follows more particularly exemplifies these embodiments.
The present invention is believed to be applicable to fluorochemical polymers for use in providing stain-resistant and/or stain-release properties to a substrate material. In particular, the present invention is directed to fluorochemical polymers that contain pendant fluoroaliphatic and cationogenic groups. While the present invention is not so limited, an appreciation of various aspects of the invention will be gained through a discussion of the examples provided below.
It is to be understood that the recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
It is to be understood that all numbers and fractions thereof are presumed to be modified by the term xe2x80x9cabout.xe2x80x9d
It is to be understood that xe2x80x9caxe2x80x9d as used herein includes both the singular and plural.
The general definitions used herein have the following meanings within the scope of the present invention.
The term xe2x80x9calkylxe2x80x9d refers to straight or branched hydrocarbon radicals, such as methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, sec-pentyl, and the like. Alkyl groups can either be unsubstituted or substituted with one or more substituents, e.g., halogen, alkoxy, aryl, arylalkyl, aralkoxy and the like. Alkyl groups include, for example, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 6 carbon atoms.
The term xe2x80x9calkenylxe2x80x9d refers to straight or branched unsaturated hydrocarbon radicals having one or more double bonds, such as ethylene, propylene, butylene, 1,3-pentadiene, 1,4-pentadiene, and the like. Alkenyl groups can either be unsubstituted or substituted with one or more substituents, e.g., haloalkyl, halogen, alkoxy, aryl, arylalkyl, aralkoxy and the like. Alkenyl groups include, for example, 2 to 12 carbon atoms, or 2 to 9 carbon atoms.
The term xe2x80x9calkylenexe2x80x9d refers to a divalent straight or branched saturated hydrocarbon radical such as, for example, xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH(CH2CH3)CH2CH(CH3)CH2xe2x80x94, and the like. Alkylene groups include, for example, 1 to 20, 1 to 12, or 1 to 4 carbon atoms.
The term xe2x80x9chaloxe2x80x9d refers to fluoride, chloride, bromide, and iodide radicals.
The term xe2x80x9chaloalkylxe2x80x9d refers to an alkyl group substituted with a halo radical as defined above.
The term xe2x80x9chydroxyalkylxe2x80x9d refers to an alkyl group as defined above substituted with a hydroxyl moiety.
The term xe2x80x9carylxe2x80x9d refers to monovalent unsaturated aromatic carbocyclic radicals having a single ring, such as phenyl, or multiple condensed rings, such as naphthyl or anthryl, which can be optionally substituted by substituents such as halogen, alkyl, arylalkyl, alkoxy, aralkoxy, and the like.
The term xe2x80x9calkoxyxe2x80x9d refers to -O-alkyl with alkyl as defined above. Alkoxy groups include, for example, methoxy, ethoxy, propoxy, isopropoxy, and the like.
The term xe2x80x9caralkylxe2x80x9d refers to an aryl radical defined as above substituted with an alkyl radical as defined above (e.g. aryl-alkyl-). Aralkyl groups include, for example, phenethyl, benzyl, and naphthethyl.
The term xe2x80x9calkarylxe2x80x9d refers to an alkyl radical defined as above bonded to an aryl radical as defined above (e.g. alkyl-aryl-).
The term xe2x80x9caralkylenexe2x80x9d refers to an aryl radical defined as above substituted with an alkylene radical as defined above, thus producing a divalent moiety (e.g. -aryl-alkyl-). Aralkylene groups include, for example, phenethyl, benzyl, and naphthethyl.
The term xe2x80x9calkarylxe2x80x9d refers to an alkyl radical defined as above bonded to an aryl radical as defined above thus producing a divalent moiety (e.g. -alkyl-aryl-).
The term xe2x80x9cweight percentxe2x80x9d refers to the percent by mass of an individual component in a total system. For example, the weight percent of an individual monomer in a polymer is the mass of the individual monomer divided by the mass of the total polymers multipled by 100.
Rf is a perfluorinated aromatic or aliphatic group containing at least one carbon atom. Where the radical contains a plurality of carbon atoms in a skeletal chain, such chain may be linear, branched, acyclic, cyclic, saturated or unsaturated. The skeletal chain of carbon atoms can be interrupted by heteroatoms, such as divalent oxygen or trivalent nitrogen atoms each of which is bonded only to carbon atoms, or hexavalent sulfur atoms each of which may be bonded to carbon, fluorine, or oxygen atoms, but preferably where such heteroatoms are present, such skeletal chain does not contain more than one said heteromoiety for every two carbon atoms.
The total number of carbon atoms in Rf can vary and be, for example, 1 to 20, preferably 1 to 8, and more preferably 1 to 4. Where Rf is or contains a cyclic structure, such structure preferably has 5 or 6 ring members, one or two of which can be said heteroatoms, e.g., oxygen and/or nitrogen. Where two or more Rf groups occur in a single formula, they can be the same or different and may be linked together to form a cyclic structure.
The term xe2x80x9ccationogenicxe2x80x9d refers to nonionic substituents capable of forming cations. Cationogenic groups include pyridinium ion, phosphonium ion, sulfonium ion, radicals of quaternary ammonium salts or cation generating amines, which include alkyl-substituted amines, amine oxides and oxygen-free amines such as, for example, xe2x80x94NH2.
The term xe2x80x9csubstantially organic solvent freexe2x80x9d refers to a solution containing less that 30% of an organic solvent.
The term xe2x80x9csubstratexe2x80x9d refers to any structural surface to which a solution may be applied such as, for example, textiles, paper, wood, leather, natural or synthetic fibers, and films.
The present invention provides for polymeric fluorochemical polymers that include perfluoroaliphatic, hydrophilic, cationogenic, and N-hydroxyalkylacrylamide and/or diacrylate monomers. Preferably the polymers comprise N-hydroxyalkylacrylamide or diacrylate monomers.
Perfluorinated monomers of the present invention include, for example, esters of the formula I 
With reference to Formula I, Rf designates a perfluoroaliphatic group. The polymeric fluorochemical polymers of the invention contain a plurality of pendent Rf groups (e.g. from 4 to 10) and contain from 5 percent to 80 percent fluorine by weight, based on the total weight of the polymer, the loci of the fluorine being essentially in the Rf groups. Additionally, polymeric fluorochemical polymers of the invention can include, for example, from 10 percent to 70 percent, 20 percent to 65 percent, or 30 percent to 60 percent fluorine by weight, based on the total weight of the polymer, the loci of the fluorine being essentially in the Rf groups. Each Rf is a stable, inert, non-polar, preferably saturated, monovalent moiety which is both oleophobic and hydrophobic. Rf contains, for example, at least 1 carbon atom. Rf can include, for example from 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 3 to 8 carbon atoms, or 3 to 6 carbon atoms. Additionally, the terminal portion of the Rf group contains a fully fluorinated terminal group such as, for example, CF3CF2CF2xe2x80x94, (CF3)2CFxe2x80x94, or the like. For example, Rf is a C3-C4 perfluoroalkyl moiety such as a C4 perfluoroalky moiety.
With reference to Formula I, xe2x80x9cAxe2x80x9d is a moiety that links the Rf groups to the acrylate group of a perfluoroaliphatic monomer. xe2x80x9cAxe2x80x9d includes, for example, from 1 to 20 carbon atoms and can optionally include caternary oxygen, nitrogen, sulfur, or silicon-containing groups or a combination thereof. Examples of A groups include, for example, a covalent bond, straight, branched or cyclic alkylene groups, arylene, alkarylene, aralkylene, oxy, oxo, thio, sulfonyl, sulfonyloxy, amino, imino, sulfonamido, carboxamido, carbonyloxy, urethanylene, urylene groups, and combinations thereof such as sulfonamidoalkylene groups. xe2x80x9cAxe2x80x9d includes, for example, a C1-C20 alkylene, xe2x80x94CzH2zxe2x80x94(OCmH2m)nxe2x80x94, 
group, each z is independently 1 to 20, m is 1 to 6, and n is 1 to 12. In an additional example, A includes a C2-C6 alkylene or 
group where z is 1 to 6. In a further example, A includes a C2-C4 alkylene group, for example xe2x80x94CH2CH2xe2x80x94, or a 
group where z is 2.
With reference to Formula I, R1 and R2 include, for example, hydrogen or C1-C12 alkyl. In an additional example, R1 and R2 include hydrogen or C1-C4 alkyl. In a further example, R1 includes hydrogen or CH3xe2x80x94 and R2 includes hydrogen, CH3xe2x80x94 or CH3CH2xe2x80x94.
Examples of perfluoroaliphatic monomers include the following:
TELOMER-Axe2x80x94(FLUOWET(trademark)-AC-812) (CH2xe2x95x90CHC(O)OCH2CH2(CF2)nCF3, where n is a value ranging from 3 to 20 and averaging 8;
(FLUOWET(trademark)-AC-600) (C6F13C2H4OC(O)CHxe2x95x90CH2)
xe2x80x94C2F5C6F10CH2OC(O)CHxe2x95x90CH2;
xe2x80x94C7F15CH2OC(O)CHxe2x95x90CH2;
xe2x80x94C7F15CON(CH3)C2H4OC(O)CHxe2x95x90CH2;
MeFOSEA xe2x80x94C8F17SO2N(CH3)C2H4OC(O)CHxe2x95x90CH2;
EtFOSEA xe2x80x94C8F17SO2N(C2H5)C2H4OC(O)CHxe2x95x90CH2;
Me FHSEA xe2x80x94C6F13SO2N(CH3)C2H4OC(O)CHxe2x95x90CH2;
MeFBSEMA xe2x80x94C4F9SO2N(CH3)C2H4OC(O)C(CH3)xe2x95x90CH2;
MeFBSEA xe2x80x94C4F9SO2N(CH3)CH2CH2OC(O)CHxe2x95x90CH2;
MeFOSEMA xe2x80x94C8F17SO2N(CH3)C2H4OC(O)C(CH3)xe2x95x90CH2, and.
HFP Trimer [(CF3)2CF]2Cxe2x95x90CHCF(CF3)2.
Hydrophilic monomers of the present invention include, for example, acrylate esters of the formula II 
With reference to Formula II, R4 includes, for example, C1-C12 alkyl, aryl, aralkyl, and alkaryl groups. In an additional example, R4 includes a C1-C8 alkyl or C1-C8 alkoxy group. In a further example, R4 includes a C1 alkyl or C1 alkoxy group.
With reference to Formula II, B is typically a moiety that links R4 to the acrylate group. B includes linking groups that may be a covalent bond, alkylene, or a group that can result from the condensation reaction of a nucleophile such as an alcohol, an amine, or a thiol with an electrophile, such as an ester, acid halide, isocyanate, sulfonyl halide, sulfonyl ester, or may result from a displacement reaction between a nucleophile and a leaving group. B contains, for example from 1 to 20 carbon atoms and can optionally contain catemary oxygen, nitrogen, sulfur, or silicon-containing groups or a combination thereof. B is preferably free of functional groups that substantially interfere with free-radical oligomerization (e.g. polymerizable olefinic double bonds, thiols, easily abstracted hydrogen atoms such as cumyl hydrogens, and other such functionality known to those skilled in the art). Examples of B groups include, for example, straight, branched or cyclic alkylene groups, arylene, alkarylene, aralkylene, oxy, oxo, thio, sulfonyl, sulfonyloxy, amino, imino, sulfonamido, carboxamido, carbonyloxy, urethanylene, urylene groups, and combinations thereof such as oxyethylene groups. B includes, for example, xe2x80x94(CH2CH2O)pxe2x80x94, where p is 1 to 25. In an additional example, B includes xe2x80x94(CH2CH2O)pxe2x80x94, where p is 10 to 20. In a further example, B includes xe2x80x94(CH2CH2O)pxe2x80x94, where p is 17.
With reference to Formula II, R3 includes, for example, hydrogen or CH3xe2x80x94.
Examples of hydrophillic monomers include the following:
CW-750A xe2x80x94CH3O(CH2CH2O)nC(O)CHxe2x95x90CH2; where navg=16
CW-450A xe2x80x94CH3O(CH2CH2O)nC(O)CHxe2x95x90CH2; where navg=9
Cationogenic monomers of the present invention include, for example, acrylate esters of the formula III 
With reference to Formula III, L designates a cationogenic group. The polymeric fluorochemical polymers of the invention contain a plurality of pendent cationogenic groups (e.g. from 4 to 10). Each cationogenic group preferably contains at least 3 carbon atoms, more preferably 3 to 20 carbon atoms, and most preferably 4 to 8 carbon atoms. Additionally, each cationogenic group optionally contains oxygen, nitrogen, or sulfur groups or a combination thereof. L includes dialkylaminoalkyl moieties, in either the free base or amine salt form, as well as quaternary ammonium and amine oxide moieties.
L is xe2x80x94(CqH2q)xe2x80x94Y, and salts thereof, including an onium moiety of the Formula V 
q is 1 to 8; Y is a cationogenic group such as, for example, the pyridinium ion, phosphonium ion, sulfonium ion, or N(R8)3 where each R8 is independently H, or C1-C4 alkyl, or where any two of R8 combine to from an alkylene moiety having 4 to 5 chain carbon atoms, or any two of R8 are xe2x80x94CH2CH2xe2x80x94 and combine with an oxygen atom to form the moiety xe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94. Xxe2x88x92 is a water-solubilizing anion and is includes alkyl sulfate ions such as, for example, CH3OSO3xe2x88x92, and the halide ions such as, for example, Clxe2x88x92, Brxe2x88x92, Fxe2x88x92, and Ixe2x88x92. Additional examples of quaternary ammonium moieties of the Formula V include those where q is 1 to 4 and each R8 is independently C1-C4 alkyl. Further examples of quaternary ammonium moieties of the Formula V include those where q is 2 and each R8 is independently C1 alkyl.
In one example, L is a dialkylaminoalkyl moiety of the Formula IV 
where q is 1 to 8, and R6 and R7 are independently C1-C12 alkyl or C1-C12 hydroxyalkyl. Additional examples of dialkylaminoalkyl moieties of the Formula IV include those where q is ito 4 and R6 and R7 are independently C1-C4 alkyl. Further examples of dialkylaminoalkyl moieties of the Formula IV include those where q is 2 and R6 and R7 are each C1 alkyl.
In a further example, L is an amine oxide moiety of the Formula VI 
where q is 1 to 8, and R9 and R10 are independently C1-C12 alkyl or C1-C12 hydroxyalkyl. Additional examples of amine oxide moieties of the Formula VI include those where q is 1 to 4 and R9 and R10 are independently C1-C4 alkyl. Further examples of amine oxide moieties of the Formula VI include those where q is 2 and R9 and R10 are each CH3.
With reference to Formula III, R5 includes hydrogen or methyl.
Examples of cationogenic monomers include the following:
DMAEMA xe2x80x94(CH3)2NC2H4OC(O)C(CH3)xe2x95x90CH2;
DEAEMA xe2x80x94(CH3CH2)2NC2H4OC(O)C(CH3)xe2x95x90CH2;
DMAEA xe2x80x94(CH3)2NC2H4OC(O)CHxe2x95x90CH2;
DEAEA xe2x80x94(CH3CH2)2NC2H4OC(O)CHxe2x95x90CH2;
xe2x80x94Clxe2x88x92(CH3)3+NC2H4OC(O)C(CH3)xe2x95x90CH2;
xe2x80x94Clxe2x88x92(CH3)3+NC2H4OC(O)CHxe2x95x90CH2;
xe2x80x94CH3SO3Oxe2x88x92(CH3)3+NC2H4OC(O)C(CH3)xe2x95x90CH2;
xe2x80x94CH3SO3Oxe2x88x92(CH3)3+NC2H4OC(O)CHxe2x95x90CH2;
xe2x80x94Clxe2x88x92H(CH3CH2)2+NC2H4OC(O)C(CH3)xe2x95x90CH2;
xe2x80x94Clxe2x88x92(CH3CH2)2+NC2H4OC(O)CHxe2x95x90CH2;
xe2x80x94Ixe2x88x92CH3(CH3CH2)2+NC2H4OC(O)C(CH3)xe2x95x90CH2; 
xe2x80x94O←N(CH3)2C2H4OC(O)C(CH3)xe2x95x90CH2; and
xe2x80x94(CH3)2N(CH2)3N(H)C(O)CHxe2x95x90CH2.
N-Hydroxyalkylacrylamide monomers of the present invention include, for example, monomers of the formula VII 
where z is 1 to 12, and R11 includes, for example, hydrogen or C1-C12 alkyl. In an additional example, z is 1 to 6, and R11 includes hydrogen or methyl.
Examples of N-hydroxyalkylacrylamides monomers include the following:
xe2x80x94HOCH2HNC(O)CHxe2x95x90CH2.
Diacrylate monomers of the present invention include, for example, monomers of the formula VIII 
where R12 includes H or CH3xe2x80x94, and R13 includes xe2x80x94(CH2CH2O)pxe2x80x94, where p is 1 to 25. In an additional example, R12 is H and p is 1 to 20. In a further example, p is 5 to 15.
Examples of diacrylate monomers include the following:
CW-400-Diacrylatexe2x80x94CH2xe2x95x90CHC(O)O(C2H4O)nC(O)CHxe2x95x90CH2; where navg=9.
The fluorochemical polymers of the present invention can be prepared by the polymerization of compounds of the Formula I, II, III, and either VII or VIII in the presence of a free-radical initiator using solvent polymerization techniques known to those of skill in the art.
The fluorochemical polymers of the present invention can be prepared in any solvent suitable for organic free-radical reactions. The reactants can be present in the solvent at any suitable concentration, e.g., from about 5 percent to about 90 percent by weight based on the total weight of the reaction mixture. Examples of suitable solvents include aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, cyclohexane), aromatic solvents (e.g., benzene, toluene, xylene), ethers (e.g., diethylether, glyme, diglyme, diisopropyl ether), esters (e.g., ethyl acetate, butyl acetate), alcohols (e.g., ethanol, isopropyl alcohol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone), sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide), halogenated solvents such as methylchloroform, FREON(trademark)113, trichloroethylene, xcex1,xcex1,xcex1.-trifluorotoluene, fluorinated ethers such as C4F9OCH3 and the like, and mixtures thereof.
Additionally, any conventional free-radical catalyst which is soluble in the solvent system can be used. Free-radical catalysts include those any of the conventional compounds such as, for example, organic azo compounds, organic peroxides (e.g., diacyl peroxides, peroxyesters, and dialkyl peroxides) that provide initiating radicals upon homolosys. Free-radical catalysts include persulfates, azo compounds such as azo bis(isobutyronitrile) and azo-2-cyanovaleric acid and the like, hydroperoxides such as cumene, t-butyl and t-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl and dicumyl peroxide, peroxyesters such as t-butyl perbenzoate and di-t-butylperoxy phthalate, diacylperoxides such as benzoyl peroxide and lauroyl peroxide. A suitable amount of free-radical catalyst depends on the particular catalyst and other reactants being used. About 0.1 percent to about 5 percent, preferably about 0.1 percent, to about 0.8 percent, and most preferably about 0.2 percent to 0.5 percent by weight of a catalyst can be used, based on the total weight of all other reactants in the reaction.
The fluorochemical polymers of the present invention can alternatively be prepared in the presence of a free-radical initiator and a chain transfer catalyst using solvent polymerization techniques known to those of skill in the art. Either functionalized or non-functionalized chain-transfer agents can be used.
Functionalized chain-transfer agents are those that contain a group capable of terminating a radical chain reaction (e.g., a sulfhydryl) yet include further functional groups capable of reacting with nucleophiles, electrophiles, or capable of undergoing displacement reactions. The nature of the functional groups on both the chain transfer agent and the monomers are chosen so that they are reactive toward one another. Examples of mutually reactive pairs include an acyl group (such as a carboxylic acid, acyl halide or ester) reacting with an alcohol or amine, an alcohol or an amine reacting with a xe2x80x9cleaving groupxe2x80x9d such as a halide or tosylate, and an isocyanate reacting with an alcohol or anine. Suitable functional groups for inclusion in the chain-transfer agent include hydroxy, amino, halo, epoxy, haloformyl, aziridinyl, acid groups and salts thereof, which react with an electrophile or nucleophile, or are capable of further transformation into such groups. Examples of such functionalized chain transfer agents include, 2-mercaptoethanol, mercaptoacetic acid, 2-mercaptobenzimidazole, 2-mercaptobenzoic acid, and 2-mercaptobenzothiazole.
Non-functionalized chain-transfer agents are those that contain a group capable of terminating a radical chain reaction (e.g., a sulfhydryl) but no further functional groups capable of reacting with nucleophiles, electrophiles, or capable of undergoing displacement reactions. Examples of such non-functionalized chain transfer agents include mono, di, and polythiols such as ethanethiol, propanethiol, butanethiol, hexanethiol, n-octylthiol, t-dodecylthiol, 2-mercaptoethyl ether, and 2-mercaptoimidazole.
Whether functionalized or not, a chain transfer agent may be present in an amount sufficient to control the number of polymerized monomer units in the oligomer. Conventional chain transfer agents useful in the synthesis of the compounds of the present invention include, for example, dodecylmercaptan and isooctyl thioglycolate in amounts of 0.1 percent to 5 percent, 0.1 percent to 2 percent, or 0.2 percent to 0.5 percent by weight of a catalyst can be used, based on the total weight of all other reactants in the reaction.
Weight ratios of the monomers of the polymeric fluorochemical compounds of the present invention, based on the total weight of the polymer include those, for example, from 20 to 70 percent by weight of a perfluoroaliphatic monomer of the Formula I, from 25 to 60 percent by weight of a hydrophilic monomer of the Formula II, from 1 to 20 percent by weight of a cationogenic monomer of the formula III, and/or 1 to 10 percent by weight of a hydroxyalkylamide monomer of the formula VII, or 0.001 to 5 percent by weight of a diacrylate monomer of the formula VIII.
In one example, weight ratios of the monomers of the polymeric fluorochemical polymers of the present invention, based on the total weight of the polymer are from 45 to 70 percent by weight of a perfluoroaliphatic monomer of the Formula I, from 25 to 50 percent by weight of a hydrophilic monomer of the Formula II, from 1 to 10 percent by weight of a cationogenic monomer of the formula III, and from 1 to 8 percent by weight of a hydroxyalkylamide monomer of the formula VII.
In a further example, weight ratios of the monomers of the polymeric fluorochemical polymers of the present invention, based on the total weight of the polymer are from 45 to 65 percent by weight of a perfluoroaliphatic monomer of the Formula I, from 30 to 50 percent by weight of a hydrophilic monomer of the Formula H, from 1 to 10 percent by weight of a cationogenic monomer of the formula III, and from 0.01 to 2 percent by weight of a diacrylate monomer of the formula VIII.
In an additional example, weight ratios of the monomers of the polymeric fluorochemical polymers of the present invention, based on the total weight of the polymer are 50 to 65 percent by weight of a perfluoroaliphatic monomer of the Formula I, 35 to 40 percent by weight of a hydrophilic monomer of the Formula II, 1 to 5 percent by weight of a cationogenic monomer of the formula III, and 1 to 5 percent by weight of a hydroxyalkylamide monomer of the formula VII.
In yet a further example, weight ratios of the monomers of the polymeric fluorochemical polymers of the present invention, based on the total weight of the polymer are 50 to 60 percent by weight of a perfluoroaliphatic monomer of the Formula I, 35 to 45 percent by weight of a hydrophilic monomer of the Formula II, 1 to 5 percent by weight of a cationogenic monomer of the formula III, and 0.1 to 1 percent by weight of a diacrylate monomer of the formula VIII.